The Effect of Atmospheric Organic Compounds on the Fe-Catalyzed S(IV) Autoxidation in Aqueous Solution

Laboratory experiments were conducted with real atmospheric aerosol particles as well as with synthetic solutions under dark conditions, to simulate some of the chemical features of aerosols. In solutions obtained by the leaching of aerosols (size range >D _ae: 0.4–1.6 m) that contained sufficient amounts of transition metal ions (e.g. Fe) and organic species (e.g. oxalate), S(IV) oxidation rates were significantly lower than those expected from the Fe-catalyzed S(IV) autoxidation in Milli-Q water. The results suggest that oxalate is responsible for much of the observed inhibition. Acetate and formate also inhibit the reaction, but to a much lesser extent. Oxalate has a strong inhibiting effect on the Fe-catalyzed S(IV) autoxidation at all investigated pH values (2.8, 3.7 and 4.5). It was established that Fe(III)-oxalato complexes affect the redox cycling of Fe(II)/Fe(III) and that the observed decrease of the reaction rate is caused by the reduced amount of catalytically active Fe(III) due to the complexation with oxalate. For the system Fe-S(IV)-O₂-oxalate at initial pH 3.7 the reaction rate was calculated using exponential simplification to account for oxalate influence on the amount of free Fe(III) by the following equation:–r_S(IV) = k · [S(IV)] · [Fe(III))] · e ^-b·[Ox]     

A forecast of public water scarcity on Leu-Rotunda Plain,Romania, for the end of the 21st century

The article examines the risk of water shortages due to the climate change on Leu-Rotunda Plain, which is part of Oltenia Plain in Romania. The region has been exposed to several extreme climatic phenomena, mostly droughts, which has created several problems related to water quality and quantity. The authors defined climate change scenarios using two regional climate models. Water resources under climate change were estimated by a regional numerical groundwater model covering a deep aquifer. The water demand components were estimated for households, industries, services, and livestock, based on specific socio-economic assumptions. A non-probabilistic risk assessment, using simplified fuzzy sets mathematics, was used to estimate water supply, water demand, and the consequences of water shortages. The results of the study revealed significant vulnerability in the water supply, a limited territorial expansion of sewerage networks, an expected increase in households’ demand, an expected increase in industrial and services water demand, a relatively stable demand for water for livestock farming, and an important water shortage in the study area. The authors conclude by highlighting a set of actions to mitigate the risk of the potential crisis.     

Late Cretaceous eclogite in the Eastern Rhodopes (Bulgaria): evidence for subduction under the Sredna Gora magmatic arc

International Journal of Earth Sciences - The Rhodopes in Bulgaria and Greece represent a nappe stack of high-grade units with polymetamorphic history. Constraining the time of metamorphism in...     

U–Pb dating, Hf-isotope characteristics and trace-REE-patterns of zircons from Medet porphyry copper deposit, Bulgaria: implications for timing, duration and sources of ore-bearing magmatism

Precise U–Pb geochronology, Hf isotope compositions and trace element distributions in zircons are combined in the present study to define the timing and sources of the magmatism forming the Medet porphyry copper deposit, Bulgaria. ID-TIMS U–Pb-zircon dating demonstrates that ore-bearing magmatism extended for less than 1.12 Ma. As inferred from the field relationships, it started with the intrusion of a quartz-monzodiorite at 90.59?±?0.29 Ma followed by granodiorite porphyries at 90.47?±?0.30 and 90.27?±?0.60 Ma and by crosscutting aplite dykes at 90.12?±?0.36 Ma. These units were overprinted by potassic alteration and host economic copper-(Mo–Au) mineralization. The main magmatic–hydrothermal activity ceased after that, and a later quartz-granodiorite porphyry dyke, dated at 89.26?±?0.32 Ma, only contains an uneconomic quartz–pyrite mineralization. Assimilation of Lower Paleozoic rocks with a mantle to mantle–crust signature is characteristic of the fertile magma in the Medet deposit, as defined by positive ?-Hf values of the inherited zircons. The positive Ce-anomalies and the higher Eu/Eu* ratios of the zircons in the mineralized Cretaceous rocks of Medet deposit argue for crystallization from a generally more oxidized magma compared to the later quartz-granodiorite porphyry dyke. A change in paleostress conditions occurred during the intrusion of the Medet pluton and its dykes. The initial stage reveals E–W extension associated with N–S compression, whereas the younger granodiorite dyke was emplaced during subsequent N–S extension. The large-scale switch of the extensional stress regime during the mineralization was favourable for ore deposition by channelling the fluids and increasing the effective permeability.     

Organic carbon and nutrient fluxes to the coastal zone from the Sepik River outflow

The Sepik River is a major contributor of water, sediment and associated organic loads to the coastal waters of northern New Guinea and the Bismarck Sea. We compare dissolved and particulate organic carbon data from September 1997 during an extremely dry El Nino year with those from 1996, 1999 and 2000 during La Nina wet season discharges. Estimated Sepik River flux of DOC is 3.2×10¹⁰ mol yr⁻¹ and POC is 1.1×10¹¹ mol yr⁻¹. The estimates for total river nutrient fluxes to the sea are 1.1×10¹⁰ mol yr⁻¹ for nitrogen and 4.6×10⁸ mol yr⁻¹ for phosphorus. The Sepik DOC flux is about equal to that combined from all four major rivers that enter the Gulf of Papua on the south coast of PNG. The Sepik inorganic PIC flux is low (1.4×10⁸ mol yr⁻¹) as the river does not drain carbonate soils. With a narrow continental shelf, and strong coastal currents, much of this exported material is available for long distance transport into the coastal Bismarck Sea and beyond.     

Macroalgal diversity along the Baltic Sea salinity gradient challenges Remane's species-minimum concept

Remane’s species-minimum concept, which states that the lowest number of taxa occurs at the horohalinicum (5-8 psu), was tested by investigating macroalgal diversity on hard substrates along the natural salinity gradient in the Baltic Sea. Field data on species occurrence and abundance were collected by SCUBA diving along 10 transects of the Finnish, Swedish and German coasts, covering a salinity range from 3.9 to 27 psu. Macroalgal species numbers declined steadily with salinity, decreasing until 7.2 psu was reached, but in the horohalinicum, a marked reduction of species number and a change in diversity were indicated by the Shannon index and evenness values. The non-linear decrease in macroalgal diversity at 5-8 psu and the lack of increase in species numbers at salinities below 5 psu imply a restricted applicability of Remane’s species-minimum concept to macroalgae.     

Mn(II)-catalysed S(IV) oxidation and its inhibition by acetic acid in acidic aqueous solutions

The kinetics of the S(IV) oxidation by oxygen in the presence of Mn(II) ions and acetic acid has been studied. Experiments were carried out at 25°C, 3.5?≤?pH?≤?5.0, [S(IV)]≈1?×?10^?3 mol/dm³, 1?×?10^?6 mol/dm³?≤?[Mn(II)]?≤?1?×?10^?5 mol/dm³, 1?×?10^?6 mol/dm³?≤?[CH₃COOH]?≤?1?×?10^?4 mol/dm³. Based on the experimental results, rate constants and orders of the reactions were determined. Depending on the reaction conditions, the observed rate constants for the Mn(II)-catalysed S(IV) oxidation ranged between 3.91?×?10^?8 and 8.89?×?10^?7 (mol/dm³) s^?1, and in the presence of acetic acid they ranged between 2.95?×?10^?8 and 7.45?×?10^?7 (mol/dm³) s^?1. The reaction order in S(IV) was zero for both reactions. The effect of Mn(II) ion and acetic acid concentrations as well as an initial pH of the solution on the S(IV) oxidation rate was discussed. It was found that the rate of the S(IV) oxidation depends on the initial pH of the solution but it is independent of the pH change during the reaction. Acetic acid has a weak inhibiting effect on the Mn(II)-catalysed S(IV) oxidation. Under the experimental conditions the S(IV) oxidation rate decreased no more than twice.     

Organic petrology, mineralogy and depositional environment of the Kipra lignite seam, Maritza-West basin, Bulgaria

The aim of the present study is to provide additional information about the properties and depositional environment of the Kipra lignite seam, which was deposited during the regressive stage of development of the Maritza-West basin. Petrographical and mineralogical data, along with ash yields and sulphur contents of 24 samples from a seam profile, have been used to study the vertical variation of the depositional settings during peat accumulation and subsequent coalification.The Kipra lignite is characterized by high ash yields and sulphur contents. It formed in a rheotrophic, low-lying mire with alkaline pH value. Vegetation with low preservation potential dominated within the palaeomire. During peat formation, frequent changes of the water level controlled the depositional environment. During the deposition of units 1 and 2, high water energy caused the transportation of high amounts of inorganic material into the mire, resulting in the formation of weakly gelified mineral-rich lignite. The organic matter from units 3 and 4 is characterized by enhanced gelification, which probably reflects the decreasing energy of the system. Good positive correlation between sulphur contents and the GI values was established in units 4, indicating that the gelification of the tissues was probably mainly controlled by the bacterial activity. In contrast, the gelification of the samples from unit 3 of the Kipra seam was probably governed by the redox conditions. The organic matter deposited under relatively wet conditions, in which the thermal and oxidative destruction of the tissues, was limited.A variety of major, minor and accessory minerals are present in Maritza-West lignite. The mineral composition is dominated mainly by pyrite, gypsum and calcite, and to a lesser extent limonite, quartz, kaolinite, montmorillonite, illite, chlorite and plagioclase. Jarosite, hematite, halloysite, mica, K-feldspar, aragonite, siderite, and dolomite were also determined in very low concentrations. These minerals formed syngenetically and epigenetically. The syngenetic stage is characterized mainly by the formation of pyrite, carbonates, silicates and sulphates, whereas the Fe-oxyhydroxides, partially the carbonates and almost all silicates are of detrital origin. During the epigenetic stage, carbonates, sulphates, clay minerals, pyrite, and Fe-oxyhydroxides were formed. Alteration products like gypsum, jarosite, limonite, chlorite, kaolinite, illite, mica, and calcite were generated due to the transformation of detrital and authigenic minerals.